Piezoelectric ceramic composition

Abstract: The present invention provides a piezoelectric ceramic composition, by which it is possible to obtain piezoelectric ceramic chip parts, having high electromechanical coupling factor and high heat-resistant property, and also good temperature coefficient of resonance frequency while maintaining high heat-resistant property, and low change over time. The piezoelectric ceramic compositions of the present invention include: a first piezoelectric ceramic composition, which is obtained by simultaneously solubilizing (Mg 1/3 Nb 2/3 )O₃ and (Yb 1/2 Nb 1/2 )O₃ as third and fourth components respectively to PbTiO₃-PbZrO₃ and is expressed by a general formula: Pb y [(Mg 1/3 Nb 2/3 ) a (Yb 1/2 Nb 1/2 ) b Ti c Zr d ] O₃ (where a + b + c + d = 1 ), and the following conditions are satisfied: 0.95 ≦ y ≦ 1.05, 0.01 ≦ a ≦ 0.15, 0.01 ≦ b ≦ 0.10, 0.30 ≦ c ≦ 0.60, 0.25 ≦ d ≦ 0.55, a second piezoelectric ceramic composition, which is obtained by substituting a part of Pb of the first piezoelectric ceramic composition with at least one element selected from Ba, Sr and Ca, a third piezoelectric ceramic composition, in which Yb treated as trivalent in the first piezoelectric ceramic composition is treated as bivalent, a fourth piezoelectric ceramic composition, which is obtained by adding at least one element selected from Cr and Mn as secondary component to the third piezoelectric ceramic composition and a fifth piezoelectric ceramic composition, which is obtained by substituting a part of Pb in the third piezoelectric ceramic composition with at least one element selected from Ba, Sr and Ca.

Description: SPECIFICATION BACKGROUND OF THE INVENTION The present invention relates to a piezoelectric ceramic composition, and in particular to a piezoelectric ceramic composition suitable for use in ceramic oscillator, ceramic discriminator, ceramic filter and surface wave elastic element. The parts used in a conventional type electronic equipment or device are lead type resin molded products, and soldering is performed by inserting lead wire of the parts into printed circuit board and by immersing the surface with no parts mounted on it into a molten solder bath. Therefore, the mounted parts are not exposed to temperature of 200°C or higher. With the progress in miniaturization of electronic equipment and devices in recent years, surface packaging and mounting are increasingly performed. To solder the parts in the surface packaging, a chip parts with no lead wire on it is provisionally mounted on a printed circuit board and the entire printed circuit board is heated in a reflow furnace. As a result, the chip parts mounted on the printed circuit board is exposed to temperature around 250°C in the reflow furnace during soldering. The materials used in conventional type piezoelectric elements include: a piezoelectric ceramic composition, in which piezoelectric property is improved by adding Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Bi 2 O 3 , etc. to a two-component ceramic composition of PbTiO 3 -PbZrO 3 to make a three-component composition, a piezoelectric ceramic composition, in which piezoelectric property is improved by adding Pb(Co 1/3 Nb 2/3 )O 3 , Pb(Mg 1/3 Nb 2/3 )O 3 , Pb(Mn 1/3 Nb 2/3 )O 3 , Pb(Ni 1/3 Nb 2/3 )O 3 , etc. to a two-component ceramic composition of PbTiO 3 -PbZrO 3 to make a three-component composition, or a three-component ceramic composition of PbTiO 3 -PbZrO 3 -Pb(Yb 1/2 Nb 1/2 )O 3 disclosed in Japanese laid-open publication No.3-36773. However, the conventional type piezoelectric element having lead wire is usually not exposed to temperature of 200°C or higher, and the ceramic composition used in these piezoelectric elements are originally not supposed to be exposed to temperature of 200°C or higher. For this reason, when these are mounted on electronic device and are exposed to temperature around 250°C in the reflow furnace for soldering, mechanical quality factor (Qm) and electromechanical coupling factor (kp) are decreased, and it is not possible to obtain piezoelectric element chip parts, which are highly reliable in heat-resistant property. Also, polarization occurs in the conventional type piezoelectric ceramic materials when these are exposed to temperature of 200°C even when the material has Curie point of 300°C or more, and piezoelectric properties such as electromechanical coupling factor are decreased. Resonance frequency is extensively deviated from initial frequency over time in a ceramic oscillator using conventional type piezoelectric material. SUMMARY OF THE INVENTION It is an object of the present invention to provide a piezoelectric ceramic composition to solve the above problems, which has the property not deteriorated even when exposed to temperature of 200°C or higher, exhibits less change over time and in which resonance frequency is not extensively deviated from initial frequency due to change overtime and which causes no problem of depolarization. To attain the above object, the present invention limits the range of product composition in each of the following compositions: a first piezoelectric ceramic composition, in which (Mg 1/3 Nb 2/3 )O 3 is solid solved as a third component and (Yb 1/2 Nb 1/2 )O 3 as a fourth component to PbTiO 3 -PbZrO 3 ; a second piezoelectric ceramic composition, which is obtained by substituting a part of Pb in the first piezoelectric ceramic composition with at least one element selected from Ba, Sr and Ca; a third piezoelectric ceramic composition, in which Yb is treated as bivalent while it is treated as trivalent in the first piezoelectric ceramic composition; a fourth piezoelectric ceramic composition, which is obtained by adding at least one element selected from Cr and Mn to the third piezoelectric ceramic composition as a secondary component; and a fifth piezoelectric ceramic composition obtained by substituting a part of Pb in the third piezoelectric ceramic composition with at least one element selected from Ba, Sr and Ca. By the use of a piezoelectric ceramic element using the piezoelectric ceramic compositions of (1) to (3) and (5) above, it is possible to obtain a piezoelectric ceramic composition, which has high electromechanical coupling factor, high heat-resistant property and exhibits low temperature coefficient of resonance frequency and less change over time. By the use of a piezoelectric ceramic compositions of (4) above, it is possible to obtain mechanical quality factor as desired without decreasing piezoelectric property while maintaining heat-resistant property and low change over time due to the secondary component. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process chart showing manufacturing of a piezoelectric chip parts using a piezoelectric ceramic composition of the present invention; and Fig. 2 is a graph showing change ratio over time of resonance frequency of the piezoelectric ceramic composition of the present invention and a conventional type piezoelectric ceramic composition. DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following, description will be given on embodiments of the present invention in connection with the drawings and the tables as attached. A piezoelectric ceramic disk using the piezoelectric ceramic composition of the present invention is manufactured through the following manufacturing processes, as given in Fig. 1: (1) Raw materials are weighed. (2) The weighed materials are processed by wet mixing in a ball mill. (3) The mixture processed by wet mixing is dried. (4) The dried material is calcinated at 750°C to 950°C. (5) The calcinated material is processed by wet crushing in a ball mill. (6) To the powder thus obtained, a proper amount of an organic binder is added to granulate it. (7) The material thus granulated is processed by pressure forming under pressure of 4 tons/cm 2 . (8) The formed material is sintered at 1130°C to 1250°C. (9) On both surfaces of the sintered product, silver electrodes are baked and mounted. (10) In silicone oil kept at 50°C to 120°C, DC electric field of 2 to 3 MV/m is applied for one hour for polarizing. As the starting materials, PbO, MgCO 3 , Yb 2 O 3 , Nb 2 O 5 , TiO 2 and ZrO 2 are used. Pb is represented by y, a mixture of MgCO 3 and Nb 2 O 5 in molar ratio of 1:1 is represented by a, a mixture of Yb 2 O 3 and Nb 2 O 5 in molar ratio of 1:1 is represented by b, Ti is represented by c, and Zr is represented by d. These are weighed to make up a product composition as shown in Table 1. In accordance with the processes already described, a piezoelectric ceramic disk of 14.3 mm in diameter and 0.6 mm in thickness was manufactured. The sample No.20A is a piezoelectric ceramic disk manufactured using a conventional type piezoelectric ceramic composition, and it is given for reference. Table 1 also summarizes the results of measurement on density (ρ), dielectric constant (ε), mechanical quality factor (Qm), electromechanical coupling factor (kp), and kp change ratio of the piezolectric ceramic disk thus manufactured. No. Composition (molar ratio) Dens'y (ρ) g/cm 3 Di- elect. Const. (ε) Mechl qual'y factor (Qm) E-mechl coupl'g factor (kp) % KP change ratio % y a b c d *1A 0.94 0.05 0.05 0.45 0.45 7.0 910 113 34.4 -20.2 2A 0.95 0.05 0.05 0.45 0.45 7.6 1508 96 60.1 -2.6 3A 1 0.05 0.05 0.45 0.45 7.7 1017 83 67.4 -2.0 4A 1.05 0.05 0.05 0.45 0.45 7.7 866 83 61.2 -2.4 *5A 1.06 0.05 0.05 0.45 0.45 7.6 753 88 34.8 -22.8 *6A 1 0.005 0.055 0.47 0.47 7.8 840 101 45.3 -18.2 7A 1 0.01 0.05 0.47 0.47 7.7 1084 85 60.7 -2.9 8A 1 0.15 0.05 0.40 0.40 7.8 725 100 61.0 -3.0 *9A 1 0.16 0.04 0.40 0.40 7.8 782 112 52.5 -16.1 *10A 1 0.095 0.005 0.45 0.45 7.8 2045 79 75.0 -16.0 11A 1 0.09 0.01 0.45 0.45 7.9 2009 78 76.3 -2.9 12A 1 0.05 0.10 0.43 0.42 7.7 866 95 60.5 -3.0 *13A 1 0.04 0.11 0.43 0.42 7.6 839 91 50.0 -18.2 *14A 1 0.10 0.05 0.29 0.55 7.6 317 392 37.4 -21.3 15A 1 0.10 0.05 0.30 0.55 7.9 439 165 60.2 -2.7 *16A 1 0.15 0.05 0.56 0.24 7.7 730 95 37.7 -8.5 17A 1 0.15 0.05 0.55 0.25 7.7 725 100 61.0 -2.8 18A 1 0.05 0.05 0.60 0.30 7.7 524 197 60.3 -3.0 *19A 1 0.05 0.05 0.61 0.29 7.6 406 252 20.2 -7.0 20A 1 0.10 0 0.45 0.45 7.7 1881 44 58.1 -20.8 The piezoelectric property, i.e. dielectric constant (ε), mechanical quality factor (Qm) and electromechanical coupling factor (kp) were calculated from the results of measurement on resonance and anti-resonance frequencies using impedance analyzer. kp change ratio is to evaluate heat-resistant property and is a value, which is obtained by immersing the disk element into a solder bath at 250°C for one minute and by measuring the change of kp. It is given by the following formula: kp change ratio (%) = [(kp - kp i ) / kp i ]× 100 where kp i is electromechanical coupling factor before immersing into solder bath, and kp is electromechanical coupling factor after immersing in solder bath for one hour. The results of the measurement were evaluated on electromechanical coupling factor (kp), and change ratio of electromechanical coupling factor. The materials were regarded as acceptable when electromechanical coupling factor was 60% or more and change ratio of electromechanical coupling factor was within ± 3%, and the other values were regarded as defective. As a result, the samples 1A, 5A, 6A, 9A, 13A, 14A, 16A and 19A were judged as defective for electromechanical coupling factor. The samples 1A, 5A, 6A, 9A, 10A, 13A, 14A, 16A and 19A were judged as defective for change ratio of electromechanical coupling factor. In the overall evaluation, the samples 2A, 3A, 4A, 7A, 8A, 11A, 12A, 15A, 17A, and 18A were judged as acceptable. In the table, the samples judged as defective are marked with the mark *. In summarizing composition range of the samples according to the results of evaluation, a sample is defective if it is within the composition range of: y < 0.95 and 1.05 < y for y; a < 0.01 and 0.15 < a for a; b < 0.01 and 0.10 < b for b; c < 0.30 and 0.60 < c for c; and d < 0.25 and 0.55 < d for d. Therefore, a sample is acceptable if it is within the composition range of: 0.95 ≦ y ≦ 1.05 for y: 0.01 ≦ a ≦ 0.15 for a; 0.01 ≦ b ≦ 0.10 for b; 0.30 ≦ c ≦ 0.60 for c; and 0.25 ≦ d ≦ 0.55 for d. As it is evident from Table 1, in the conventional type piezoelectric ceramic composition, change ratio of electromechanical coupling factor due to soldering heat at 250°C is around -20%, while, in the piezoelectric ceramic composition of the present invention, it can be extensively improved to -3.0% to -2.0% or less by simultaneously solubilizing (Mg 1/3 Nb 2/3 )O 3 and (Yb 1/2 Nb 1/2 )O 3 as the third and the fourth components respectively to PbTiO 3 -PbZrO 3 . Fig. 2 shows the change of resonance frequency over time of the sample 3A, which is an embodiment of the present invention, and a conventional example, i.e. the sample No.20A. The change ratio of resonance frequency is given by the following formula: Change ratio of resonance frequency (%) = [(fr - fr i ) / fr i ] × 100 where fr i represents resonance frequency in initial stage (one hour after polarization), and fr represents resonance frequency at a certain period of time after polarization. As it is evident from this figure, compared with the conventional type piezoelectric ceramic composition, the change ratio of resonance frequency of the piezoelectric ceramic composition of the present invention can be reduced to 0.1% / time decade or lower. Next, description will be given on a piezoelectric ceramic composition, which is obtained by substituting a part of Pb in the starting materials with Me, i.e. Ba, Sr or Ca. The composition ratio of Pb and Me is represented by (1 - x) and x respectively. Using the piezoelectric ceramic composition obtained by substituting a part of Pb with Me as shown in Table 2, a piezoelectric ceramic disk of the same shape, i.e. 14.3 mm in diameter and 0.6 mm in thickness, was produced by the manufacturing processes described above. On this piezoelectric ceramic disk, density (ρ), dielectric constant (ε), mechanical quality factor (Qm) and electromechanical coupling factor (kp) were determined by the same measuring procedure. Further, temperature coefficient of resonance frequency (frTC) was measured. Temperature coefficient of resonance frequency (frTC) is given by the following formula: frTC (ppm / °C ) = [(fr 1 - fr 2 ) / (fr 3 × 125)] × 10 6 where fr 1 and fr 2 represent maximum value and minimum value of resonance frequency in temperature range of -40°C to 85°C respectively, and fr 3 represents resonance frequency at 25°C. The sample No.25B is a piezoelectric ceramic disk obtained by the use of a conventional type piezoelectric ceramic composition, and it is given for reference. Table 2 summarizes product composition of the piezoelectric ceramic compositions thus obtained and the results of measurements on the piezoelectric ceramic disk. No. Subs'te element Comp'n (molar ratio) Basic Composition (molar ratio) Dens'y (ρ) g/cm 3 Di- elect. Const. (ε) Mechl qual'y factor (Qm) E-mechl coupl'g factor (kp) % kp change ratio % Temp're co-effic't (frTC) ppm/°C Me x a b c d *1B -- 0 0.05 0.05 0.45 0.45 7.7 1017 83 67.4 -2.0 356 2B Ba 0.01 0.05 0.05 0.45 0.45 7.7 1161 82 64.1 -2.1 150 3B Ba 0.05 0.05 0.05 0.45 0.45 7.7 1180 80 63.8 -2.0 149 4B Ba 0.12 0.05 0.05 0.45 0.45 7.6 1204 61 63.3 -2.4 141 *5B Ba 0.13 0.05 0.05 0.45 0.45 7.2 1364 70 50.4 -21.8 132 6B Sr 0.05 0.05 0.05 0.45 0.45 7.6 1233 92 63.1 -2.2 125 7B Ca 0.05 0.05 0.05 0.45 0.45 7.6 1256 90 60.1 -2.1 126 8B Ba 0.08 0.05 0.05 0.45 0.45 7.7 1204 87 63.7 -2.2 143 9B Sr 0.08 0.05 0.05 0.45 0.45 7.6 1301 101 62.5 -2.3 121 10B Ca 0.08 0.05 0.05 0.45 0.45 7.6 1398 91 60.3 -2.1 120 *11B Ba 0.05 0.005 0.055 0.47 0.47 7.7 821 98 44.8 -20.4 155 12B Ba 0.05 0.01 0.05 0.47 0.47 7.7 1197 88 60.2 -2.8 150 13B Ba 0.05 0.15 0.05 0.40 0.40 7.7 833 95 61.0 -2.9 148 *14B Ba 0.05 0.16 0.04 0.40 0.40 7.7 801 104 50.1 -19.6 153 *15B Ba 0.05 0.095 0.005 0.45 0.45 7.7 2095 81 66.6 -17.3 154 16B Ba 0.05 0.09 0.01 0.45 0.45 7.7 2012 84 67.8 -3.0 150 17B Ba 0.05 0.05 0.10 0.43 0.42 7.6 866 95 60.5 -2.9 151 *18B Ba 0.05 0.04 0.11 0.43 0.42 7.5 855 106 48.7 -22.9 147 *19B Ba 0.05 0.10 0.05 0.29 0.56 7.5 423 341 32.6 -22.4 135 20B Ba 0.05 0.10 0.05 0.30 0.55 7.6 595 121 60.2 -2.8 137 *21B Ba 0.05 0.15 0.05 0.56 0.24 7.6 780 99 35.4 -9.6 145 22B Ba 0.05 0.15 0.05 0.55 0.25 7.6 820 103 61.1 -2.9 144 23B Ba 0.05 0.05 0.05 0.60 0.30 7.6 650 154 60.5 -2.7 149 *24B Ba 0.05 0.05 0.05 0.61 0.29 7.5 488 264 30.3 -8.4 156 25B -- 0 0.10 0 0.45 0.45 7.7 1881 44 56.1 -20.8 368 The results of the measurement were evaluated on temperature coefficient of resonance frequency (frTC). Similarly to the case of the piezoelectric ceramic disk of Table 1, the materials were regarded as acceptable when kp was 60% ormore and kp change ratio was within ± 3% and the materials with other values were regarded as defective except that the materials were regarded as acceptable when temperature coefficient of resonance frequency was 200 ppm or less and the materials with the other values were regarded as defective. As a result, the samples 5B, 11B, 18B, 19B, 21B and 24B were judged as defective for electromechanical coupling factor. The samples 5B, 11B, 14B, 15B, 18B, 19B, 21B and 24B were judged as defective for change ratio of electromechanical coupling factor, and the sample 1B was judged as defective for temperature coefficient of resonance frequency. In the overall evaluation, the samples 2B, 3B, 4B, 6B, 7B, 8B, 9B, 10B, 12B, 13B, 16B, 17B, 20B, 22B and 23B were judged as acceptable. In summarizing composition range of the samples according to the results of evaluation, a sample is defective if it is within the composition range of: 0.12 < x for x; a < 0.01 and 0.15 < a for a; b < 0.01 and 0.10 < b for b; c < 0.30 and 0.60 < c for c; and d < 0.25 and 0.55< d for d. Therefore, a sample is acceptable if it is within the composition range of: 0 < x ≦ 0.12 for x; 0.01 ≦ a ≦ 0.15 for a; 0.01 ≦ b ≦ 0.10 for b; 0.30 ≦ c ≦ 0.60 for c; and 0.25 ≦ d ≦ d. 0.55 for As it is evident from Table 2, by substituting a part of Pb with at least one element selected from Ba, Sr and Ca, it is possible to extensively improve temperature coefficient of resonance frequency (frTC) without decreasing heat-resistant property and the change over time. When the change of resonance frequency over time was determined on the sample No.3B, the value was as low as 0.1% / time decade or less as in the case of the sample No.3A in Fig. 1. In general, in producing a piezeoelectric ceramic composition, it is widely known that it is possible to blend the materials to match stable valence of the element used in case a plurality of stable valence states of the elements used are present, i.e. in case it is possible to constitute oxides in a purality of oxidation statuses. For example, in a three-component type piezoelectric material using Mn and Nb as the third components, PbTiO 3 -PbZrO 3 -Pb(Mn 1/3 Nb 2/3 )O 3 having valence of Mn as bivalent and PbTiO 3 -PbZrO 3 -Pb(Mn 1/2 Nb 1/2 )O 3 having valence of Mn as trivalent are both used in practical application. The present inventors have found that Yb used in the above embodiment is an element, which may be bivalent or trivalent as stable valence, while, even when it is treated as bivalent, the effect of the present invention can be attained. In the following, description will be given on a piezoelectric ceramic disk using a piezoelectric ceramic composition, which has Yb as bivalent. This piezoelectric ceramic disk is produced by the same procedure as described above, except that the materials are sintered at 1100°C to 1260°C. As the starting materials, PbO, MgCO 3 , Yb 2 O 3 , Nb 2 O 5 , TiO 2 and ZrO 2 were used. Mg 1/3 · Nb 2/3 was represented by e, Yb 1/3 · Nb 2/3 was represented by f, Pb · Ti was represented by g, and Pb · Zr was represented by h. These materials were weighed to make up a product composition shown in Table 3. In accordance with the processes described above, a piezoelectric ceramic disk of 15 mm in diameter and 1 mm in thickness was manfuactured. On each of the piezoelectric ceramic disks thus obtained, density, electromechanical coupling factor, dielectric constant and mechanical quality factor were determined. Table 3 summarizes composition of the piezoelectric ceramic compositions thus obtained and the results of measurement on the piezoelectric ceramic disks. No. Composition (molar ratio) Dens'y (ρ) g/cm 3 Di- elect. const. (ε) Mechl qual'y factor (Qm) E-mechl coupl'g factor (kp) % KP change ratio % e f g h 1C 0.06 0.06 0.44 0.44 7.8 1150 85 62.5 -2.0 *2C 0.005 0.065 0.47 0.46 7.5 950 90 46.0 -19.5 3C 0.01 0.06 0.47 0.46 7.7 1100 85 60.5 -3.0 4C 0.15 0.05 0.42 0.38 7.7 1020 90 61.0 -3.0 *5C 0.16 0.04 0.42 0.38 7.5 850 100 45.5 -18.5 *6C 0.095 0.005 0.44 0.46 7.5 1250 85 60.0 -18.0 7C 0.09 0.01 0.44 0.46 7.8 1300 100 65.0 -2.5 8C 0.05 0.15 0.42 0.38 7.7 1010 90 60.5 -3.0 *9C 0.04 0.16 0.42 0.38 7.3 890 95 48.0 -19.0 *10C 0.11 0.06 0.25 0.58 7.4 750 300 40.0 -22.0 11C 0.11 0.06 0.30 0.53 7.7 1000 100 60.0 -3.0 *12C 0.15 0.06 0.56 0.23 7.4 780 90 38.0 -12.0 13C 0.15 0.06 0.54 0.25 7.7 1010 95 60.5 -2.7 14C 0.07 0.03 0.60 0.30 7.7 1000 110 60.2 -3.0 *15C 0.07 0.03 0.61 0.29 7.4 730 200 30.5 -9.5 The results of the measurement were evaluated by the same procedure as the piezoelectric ceramic disks shown in Table 1. The materials were regarded as acceptable when kp was 60% or more and kp change ratio was within ± 3%, and the materials with the other values were regarded as defective. As a result, the samples 2C, 5C, 9C, 10C, 12C and 15C were judged as defective for electromechanical coupling factor. The samples 2C, 5C, 6C, 9C, 10C, 12C and 15C were judged as defective for change ratio of electromechanical coupling factor. In the overall evaluation, the samples 1C, 3C, 4C, 7C, 8C, 11C, 13C and 14C were judged as acceptable. In summarizing composition range of the samples according to the results of evaluation, a sample is defective if it is within the composition range of: e < 0.01 and 0.15 < e for e; f < 0.01 and 0.15 < f for f; g < 0.30 and 0.60 < g for g; and h < 0.25 and 0.58 ≦ h for h. Therefore, a sample is acceptable if it is within the composition range of: 0.01 ≦ e ≦ 0.15 for e; 0.01 ≦ f ≦ 0.15 for f; 0.30 ≦ g ≦ 0.60 for g; and 0.25 ≦ h < 0.58 for h. Specifically, 1. In case e < 0.01, sintering property of the element is aggravated, and high electromechanical coupling factor as desired is not obtained and also heat-resistant property is decreased. Heat-resistant property is also decreased when 0.15 < e. 2. In case f < 0.01, heat-resistant property is decreased. In case 0.15 < f, sintering property is decreased, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also aggravated. 3. In case g < 0.30 and 0.60< g, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also decreased. 4. In a composition with h < 0. 25, high electromechanical coupling factor as desired is not obtained. Further, in case d > 0.58, the effect to improve heat-resistant property is not obtained. As it is evident from Table 3, in the conventional type piezoelectric ceramic composition, change ratio of electromechanical coupling factor due to soldering heat at 250°C is around -20%, while, in the piezoelectric ceramic composition of the present invention, it can be extensively improved to -3% or less by simultaneously solubilizing (Mg 1/3 Nb 2/3 )O 3 and (Yb 1/3 Nb 2/3 )O 3 as the third and the fourth components respectively to PbTiO 3 -PbZrO 3 . When the change of resonance frequency over time was determined on the sample No.1E, the value was as low as 0.1% / time decade or less as in the case of the sample No.3A in Fig.2. Next, description will be given on a piezoelectric ceramic disk using the piezoelectric ceramic composition, which contains Cr 2 O 3 and MnO 2 added as secondary components to the piezoelectric composition having Yb as bivalent, referring to Table 4. The piezoelectric ceramic composition used for this piezoelectric ceramic disk is produced through the manufacturing processes shown in Fig. 1 except that Cr 3 O 3 and MnCO 3 are added as the starting materials to the piezoelectric ceramic composition shown in Table 3 to make up product composition shown in Table 3. Thus, detailed description is not given here. Table 4 also summarizes the results of the measurement on density (ρ), dielectric constant (ε), mechanical quality factor (Qm), electromechanical coupling factor (kp) and change ratio of electromechanical coupling factor (kp) of each of the piezoelectric ceramic disks. No. Composition (molar ratio) Second'y element (Wt %) Dens'y (ρ) g/cm 3 Di- elect. Const. (ε) Mechl qual'y factor (Qm) E-mechl coupl'g factor (kp) % KP change ratio % e f g h Cr 2 O 3 MnO 2 *1D 0.06 0.06 0.44 0.44 -- 0.005 7.8 1150 85 62.3 -- 2D 0.06 0.06 0.44 0.44 -- 0.02 7.7 1160 1000 62.0 -1.9 3D 0.06 0.06 0.44 0.44 -- 0.9 7.7 1200 1550 64.5 -1.5 4D 0.06 0.06 0.44 0.44 -- 1.8 7.7 1250 1100 62.2 -3.0 *5D 0.06 0.06 0.44 0.44 -- 2.3 7.4 810 400 49.6 -20.0 6D 0.06 0.06 0.44 0.44 0.2 -- 7.8 1160 510 63.5 -2.0 7D 0.06 0.06 0.44 0.44 0.4 -- 7.8 1190 760 63.0 -2.0 8D 0.06 0.06 0.44 0.44 0.3 0.5 7.8 1210 1400 64.1 -1.8 *9D 0.005 0.065 0.47 0.46 -- 0.9 7.5 940 490 47.3 -18.5 10D 0.01 0.06 0.47 0.46 -- 0.9 7.7 1110 1050 60.4 -2.8 11D 0.15 0.05 0.42 0.38 -- 0.9 7.8 1050 1250 62.1 -2.5 *12D 0.16 0.04 0.42 0.38 -- 0.9 7.5 870 900 50.0 -17.9 *13D 0.095 0.005 0.44 0.46 -- 0.9 7.5 1250 1100 60.2 -17.1 14D 0.09 0.01 0.44 0.46 -- 0.9 7.8 1340 1320 66.4 -2.4 15D 0.05 0.15 0.42 0.38 -- 0.9 7.7 1020 1370 61.5 -2.8 *16D 0.05 0.05 0.45 0.45 0.3 -- 7.4 910 1150 48.2 -20.5 *17D 0.11 0.06 0.25 0.58 -- 0.9 7.4 800 1050 46.1 -21.0 18D 0.11 0.06 0.30 0.53 -- 0.9 7.6 1030 1300 60.3 -2.5 *19D 0.15 0.06 0.56 0.23 -- 0.9 7.4 770 950 41.2 -12.5 20D 0.15 0.06 0.54 0.25 -- 0.9 7.7 1040 1100 61.0 -2.7 21D 0.07 0.03 0.60 0.30 -- 0.9 7.6 1010 1100 60.4 -2.7 *22D 0.07 0.03 0.61 0.29 -- 0.9 7.4 750 850 33.3 -11.2 The results of the measurement were evaluated for kp and kp change ratio by the same procedure as the piezoelectric ceramic dsiks of Table 1. The materials were regarded as acceptable when kp was 60% or more and kp change ratio was within ± 3%, and the materials with the other values were regarded as defective. As a result, the samples 5D, 9D, 12D, 16D, 17D, 19D and 22D were judged as defective for electromechanical coupling factor. The samples 1D, 5D, 9D, 12D, 13D, 16D, 17D, 19D and 22D were judged as defective for change ratio of electromechanical coupling factor. In the overall evaluation, the samples 2D, 3D, 4D, 6D, 7D, 8D, 10D, 11D, 14D, 15D, 18D, 20D and 21D were judged as acceptable. In summarizing composition range of the samples according to the results of evaluation, a sample is defective if it is within the composition range of: e < 0.01 and 0.15 < e for e; b < 0.01 and 0.15 < b for b; c < 0.30 and 0.60 < c for c; and d < 0.25 and 0.58 ≦ d for d. Therefore, a sample is acceptable if it is within the composition range of: 0.01 ≦ e ≦ 0.15 for e; 0.01 ≦ b ≦ 0.15 for b; 0.30 ≦ c ≦ 0.60 for c; and 0.25 ≦ d < 0.58 for d. Specifically, 1. In case e < 0.01, sintering property of the element is aggravated, and high electromechanical coupling factor as desired is not obtained and also heat-resistant property is decreased. Heat-resistant property is also decreased when 0.15 < e. 2. In case f < 0.01, heat-resistant property is decreased. In case 0.15 < f, sintering property is decreased, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also aggravated. 3. In case g < 0.30 and 0.60 < g, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also decreased. 4. In a composition with h < 0.25, high electromechanical coupling factor as desired is not obtained. Further, in case h > 0.58, the effect to improve heat-resistant property is not obtained. 5. In case at least one element selected from Cr and Mn is added by 0.02 to 1.8 weight % as converted respectively as secondary components, it is possible to improve mechanical quality factor (Qm) without decreasing piezoelectric property while improving heat-resistant property and the change over time. If Cr 2 O 3 and MnO 2 as secondary components are added by less than 0.02 weight %, Qm cannot be improved. If these are added by more than 1.8 weight %, heat-resistant property is decreased. Further, by selecting composition ratio, it is possible to obtain a piezoelectric ceramic material having mechanical quality factor of 500 or more without decreasing piezoelectric property from the materials having electromechanical coupling factor of 60% or more. Next, description will be given on a piezoelectric ceramic composition, which is obtained by substituting a part of Pb in the piezoelectric ceramic composition having Yb as bivalent with Ba, Sr or Ca. The compositions of Pb and Me are represented by (1 - x) and x respectively. Using a piezoelectric ceramic composition of Table 2 obtained by substituting a part of Pb with Me, a piezoelectric ceramic disk of 15 mm in diameter and 1 mm in thickness was manufactured by the manufacturing processes as described above. On each of the piezoelectric ceramic disks, density (ρ), dielectric constant (ε), and electromechanical coupling factor (kp) were determined by the same procedure. Further, temperature coefficient of resonance frequency (frTC) and mechanical quality factor (Qm) were measured. Table 5 summarizes composition of the piezoelectric ceramic composition thus obtained and the results of measurement on the piezoelectric ceramic disks. The composition of Me is represented by x. No. Subs'te element Comp'n (molar ratio) Basic composition (molar ratio) Dens'y (ρ) g/cm 3 Di- elect. const. (ε) Mechl qual'y factor (Qm) E-mechl coupl'g factor (kp) % kp change ratio % Temp're co-effic't (frTC) ppm/°C Me x e f g h *1E -- 0 0.06 0.06 0.44 0.44 7.8 1150 85 62.5 -2.0 340 2E Sr 0.01 0.06 0.06 0.44 0.44 7.7 1150 85 63.0 -2.1 130 3E Sr 0.05 0.06 0.06 0.44 0.44 7.7 1200 80 64.1 -2.0 120 4E Sr 0.12 0.06 0.06 0.44 0.44 7.6 1250 80 63.0 -2.5 120 *5E Sr 0.15 0.06 0.06 0.44 0.44 7.0 1380 75 49.5 -22.0 140 6E Ba 0.05 0.06 0.06 0.44 0.44 7.7 1240 95 62.0 -2.3 140 7E Ca 0.05 0.06 0.06 0.44 0.44 7.6 1270 90 61.3 -2.2 110 8E Ba 0.08 0.05 0.06 0.44 0.44 7.7 1170 90 63.1 -2.4 130 9E Sr 0.08 0.06 0.06 0.44 0.44 7.6 1320 95 60.5 -2.2 110 10E Ca 0.08 0.06 0.06 0.44 0.44 7.6 1400 90 60.2 -2.3 105 *11E Sr 0.05 0.005 0.065 0.47 0.46 7.5 960 95 46.2 -21.5 150 12E Sr 0.05 0.01 0.06 0.47 0.46 7.7 1160 85 60.5 -2.9 140 13E Sr 0.05 0.15 0.05 0.42 0.38 7.7 1020 95 61.0 -3.0 140 *14E Sr 0.05 0.16 0.04 0.42 0.48 7.5 900 100 47.0 -19.5 130 *15E Sr 0.05 0.095 0.005 0.44 0.46 7.6 1340 90 60.7 -19.0 140 16E Sr 0.05 0.09 0.01 0.44 0.46 7.7 1400 100 66.7 -3.0 130 17E Sr 0.05 0.05 0.15 0.42 0.38 7.7 1030 95 60.2 -2.9 130 *18E Sr 0.05 0.04 0.16 0.42 0.38 7.2 920 95 49.0 -21.9 140 *19E Sr 0.05 0.11 0.06 0.25 0.58 7.4 770 305 40.8 -22.5 130 20E Sr 0.05 0.11 0.06 0.30 0.53 7.6 1010 100 60.1 -3.0 120 *21E Sr 0.05 0.15 0.06 0.56 0.23 7.3 810 95 40.2 -13.5 140 22E Sr 0.05 0.15 0.06 0.54 0.25 7.6 1010 100 60.0 -2.9 130 23E Sr 0.05 0.07 0.03 0.60 0.30 7.6 1000 115 60.5 -3.0 130 *24E Sr 0.05 0.07 0.03 0.61 0.29 7.3 740 210 31.0 -10.5 140 The results of the measurement were evaluated by the same procedure as in Table 2. Similarly to the piezoelectric ceramic disks shown in Table 1, the disks were regarded as acceptable when kp was 60% or more and kp change ratio was within ± 3% and the disks with other values were regarded as defective except that the materials were regarded as acceptable when temperature coefficient of resonance frequency (frTC) was 200 ppm or less and the materials with the other values were regarded as defective. As a result, the samples 11E, 14E, 18E, 19E, 21E and 24E were judged as defective for electromechanical coupling factor. The samples 5E, 11E, 14E, 15E, 18E, 19E, 21E and 24E were judged as defective for change ratio of electromechanical coupling factor. The sample 1E was judged as defective for temperature coefficient of resonance frequency. In the overall evaluation, the samples 2E, 3E, 4E, 6E, 7E, 8E, 9E, 10E, 12E, 13E, 16E, 17E, 20E, 22E and 23E were judged as acceptable. In summarizing composition range of the samples according to the results of evaluation, a sample is defective if it is within the composition range of: x < 0.01 and 0.12 < x for x; e < 0.01 and 0.15 < e for e; f < 0.01 and 0.15 < f for f; g < 0.30 and 0.60 < g for g; and h < 0.25 and 0.58 ≦ h for h. Therefore, a sample is acceptable if it is within the composition range of: 0 < x ≦ 0.12 for x; 0.01 ≦ e ≦ e; 0.15 for 0.01 ≦ f ≦ 0.15 for f; 0.30 ≦ g ≦ 0.60 for g; and 0.25 ≦ h < 0.58 for h. Specifically, 1. In case e < 0.01, sintering property of the element is aggravated, and high electromechanical coupling factor as desired is not obtained and also heat-resistant property is decreased. Heat-resistant property is also decreased when 0.15 < e. 2. In case f < 0.01, heat-resistant property is decreased. In case 0.15 < f, sintering property is decreased, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also aggravated. 3. In case g < 0.30 and 0.60 < g, high electromechanical coupling factor as desired is not obtained, and heat-resistant property is also decreased. 4. In a composition with h < 0.25, high electromechanical coupling factor as desired is not obtained. Further, in case h > 0.58, the effect to improve heat-resistant property is not obtained. 5. In case a part of Pb is substituted with at least one of Ba, Sr or Ca, temperature coefficient of resonance frequency (fr) is increased without decreasing heat-resistant property and change over time. In case Me is 0, temperature coefficient of resonance frequency cannot be increased. If it is more than 0.12, heat-resistant property is decreased. Thus, it is preferred that 0< x ≦ 0.12. As it is evident from Table 5, in the conventional type piezoelectric ceramic composition, change ratio of electromechanical coupling factor due to soldering heat at 250°C is around -20%, while, in the piezoelectric ceramic composition of the present invention, it can be extensively improved to -2.0% to -3.0% by simultaneously solubilizing (Mg 1/3 Nb 2/3 )O 3 and (Yb 1/3 Nb 2/3 )O 3 as the third and the fourth components respectively to PbTiO 3 -PbZrO 3 . Further, by substituting a part of Pb with at least one of Ba, Sr, or Ca, it is possible to extensively improve temperature coefficient of resonance frequency (frTC) without decreasing heat-resistant property and the change over time. When the change of resonance frequency over time was determined on the sample No.3E, the value was as low as 0.1% / time decade or less similarly to the case of the sample No.3A of Fig. 2. As it is self-explanatory from the above description, it is possible by the use of the piezoelectric ceramic composition of the present invention to provide a piezoelectric ceramic element, which has high electromechanical coupling factor (kp), high heat-resistant property and exhibits better temperature coefficient of resonance frequency with improved heat-resistant property and with extremely low change over time. Therefore, it is possible to manufacture chip parts, in which piezoelectric property is not decreased even when exposed to temperature around 250°C during surface packaging. In the examples described above, the starting materials are oxides or carbonates, while similar effects can be obtained when carbonates, organic acid salts or hydroxides are used instead of the oxides, and oxides, organic acid salts or hydroxides are used instead of the carbonates.

Claims: A piezoelectric ceramic composition, expressed by a general formula: Pb y [(Mg 1/3 Nb 2/3 ) a (Yb 1/2 Nb 1/2 ) b Ti c Zr d ]O 3 (where a + b + c + d = 1), and the following conditions are satisfied: 0.95 ≦ y ≦ 1.05 0.01 ≦ a ≦ 0.15 0.01 ≦ b ≦ 0.10 0.30 ≦ c ≦ 0.60 0.25 ≦ d ≦ 0.55. A piezoelectric ceramic composition, expressed by a general formula: (Pb 1-x Me x )[(Mg 1/3 Nb 2/3 ) a (Yb 1/2 Nb 1/2 ) b Ti c Zr d ]O 3 (where Me represents at least one element selected from Ba, Sr and Ca, and a + b + c + d = 1), and the following conditions are satisfied: 0 < x ≦ 0.12 0.01 ≦ a ≦ 0.15 0.01 ≦ b ≦ 0.10 0.30 ≦ c ≦ 0.60 0.25 ≦ d ≦ 0.55. A piezoelectric ceramic composition, expressed by a general formula: Pb[(Mg 1/3 Nb 2/3 ) e (Yb 1/3 Nb 2/3 ) f Ti g Zr h ]O 3 (where e + f + g + h = 1), and the following conditions are satisfied: 0.01 ≦ e ≦ 0.15 0.01 ≦ f ≦ 0.15 0.30 ≦ g ≦ 0.60 0.25 ≦ h < 0.58. A piezoelectric ceramic composition, comprising a composition expressed by a general formula: Pb[(Mg 1/3 Nb 2/3 ) e (Yb 1/3 Nb 2/3 ) f Ti g Zr h ]O 3 (where e + f + g + h = 1), and the following conditions are satisfied: 0.01 ≦ e ≦ 0.15 0.01 ≦ f ≦ 0.15 0.30 ≦ g ≦ 0.60 0.25 ≦ h < 0.58. as basic component, and at least one element selected from Cr and Mn as secondary component, said selected elements being added by 0.02 to 1.8 weight % as converted to Cr 2 O 3 and MnO 2 respectively. A piezoelectric ceramic composition, expressed by a general formula: (Pb 1-x Me x )[(Mg 1/3 Nb 2/3 ) e (Yb 1/3 Nb 2/3 ) f Ti g Zr h ]O 3 (where Me represents at least one element selected from Ba, Sr and Ca, and e + f + g + h = 1), and the following conditions are satisfied: 0 < x ≦ 0.12 0.01 ≦ e ≦ 0.15 0.01 ≦ f ≦ 0.15 0.30 ≦ g ≦ 0.60 0.25 ≦ h < 0.58.

Inventors: KAMIHARA MASAHARU, OTSU SATOSHI, YAMANE FUMIKAZU, KAMIHARA, MASAHARU, OTSU, SATOSHI, YAMANE, FUMIKAZU
Applicants: TDK CORP, TDK CORPORATION
Application year: 1994
Main classification: H01L41
IPC codes: H01L41